Aromatic polymers prepared from halophenols containing keto groups

ABSTRACT

New aromatic polymers comprising units of the formula ##STR1## and copolymers comprising such units or other units such as ##STR2## The new polymer may be made from the alkali metal salt of a halophenol of the formula ##STR3##

This is a continuation, of application Ser. No. 271,209 filed July 12, 1972, and now abandoned.

This invention relates to new aromatic polymers and to new chemical intermediates from which they may be produced.

According to the present invention there are provided new aromatic polymers whose molecular chains comprise units of the formula ##STR4## either alone or copolymerised with other units, and in particular with units of the formulae ##STR5## and ##STR6## According to the invention there are also provided, as new chemical intermediates, halophenols of the formula ##STR7## (where X is halogen) and their alkali metal salts.

These halophenols possess a reactive halogen atom as well as a phenolic group and can serve as valuable intermediates for preparing a variety of products; for example the halogen atom can be replaced by amino and substituted amino groups or by oxygen- or sulphur-containing anions to produce amines, ethers and sulphides.

The halophenols of the invention may be made by either of the reaction sequences outlined below, the second being the more convenient. ##STR8##

The halophenol can be converted into an alkali metal salt by treatment with a suitable base (e.g. an alkali metal hydroxide or alkoxide). Conveniently hydrolysis of carbonate phenol precursor and subsequent conversion to alkali metal salt of the phenol is carried out in a single step.

The alkali metal salts of the halophenols polymerise at 150°-400° C. by displacement of alkali metal halide to give polymers according to the invention having units of the formula ##STR9##

They may be polymerised alone; or they may be copolymerised with alkali metal salts of other activated halophenols (or with mixtures of activated dihalobenzenoid compounds and an equivalent amount of alkali metal hydroxide) and in particular alkali metal salts of halophenols of the formula ##STR10## as described in British specifications 1 153 035, 1 177 183 and 1 234 301; and with the alkali metal salts of halophenols having the formula ##STR11## as described in Dutch Application 70 11346, or they may be copolymerised with mixtures of alkali metal salts of dihydric phenols and activated dihalobenzenoid compounds as described in British specifications 1 078 234 and 1 133 561. The halogen atoms in the halophenol or dihalobenzenoid compound are activated by electron-attracting groups such as --SO₂ -- ortho or para to the halogen atom.

In a further embodiment of the invention, block copolymers may be formed by polymerising an alkali metal salt of a halophenol of the formula ##STR12## in the presence of preformed polymers comprising benzenoid groups and oxygen or sulphur atoms in the polymer chain, with bivalent electron-attracting groups such as --SO₂ -- or --CO-- also in the polymer chain separated from an oxygen or sulphur atom by a para or ortho phenylene group, such as for example those described in British specifications 1 078 234 and 1 153 035 and U.S. Pat. No. 3 432 468. Preferred preformed polymers are those having repeating units ##STR13## either alone or copolymerised with each other and/or up to 80% of units having the formula ##STR14##

The halogen atoms are preferably chlorine or fluorine. The fluorine derivatives generally are more reactive and enable the displacement of alkali metal halide to be carried out more quickly or at a lower temperature, but are more expensive. Bromine derivatives are also relatively expensive and although they resemble the chlorine derivatives in performance they offer no advantages. Iodine derivatives are generally less suitable.

The alkali metal is conveniently potassium or sodium. Displacement of alkali metal halide often occurs more readily if the potassium cation is present in the reagent used, but the weight (and usually the price) per mole of a potassium compound is higher than for the corresponding sodium compound. Some or all of the alkali metal cation in the reagent may be replaced by an organic onium cation having a positively charged hetero-atom (for example a quaternary ammonium cation such as tetramethyl-ammonium) stable under the conditions of the reaction, and the term "alkali metal salt" as used herein is deemed to refer also to salts containing such onium cations.

The polymerisation is preferably carried out in a polar liquid which is a solvent for alkali metal phenoxides and is stable under the reaction conditions employed, although an alkali metal salt of a 4-(4-halobenzoyl)-4'-hydroxybiphenyl may also be polymerised or copolymerised with another alkali metal salt of a halophenol in the melt.

Suitable polar liquids for the reaction include the lower dialkyl and cyclic alkylene sulphoxides and sulphones (e.g. dimethyl sulphoxide and 1,1-dioxothiolan), aromatic nitriles (e.g. benzonitrile) and diaryl ketones (e.g. benzophenone), sulphoxides and sulphones (e.g. diphenyl sulphone). The total amount of solvent used is desirably sufficient to ensure that none of the starting materials are in the solid state in the reaction mixture.

For example, dimethyl sulphoxide is a convenient solvent but cannot be used at such high temperatures as 1,1-dioxothiolan or diphenyl sulphone.

The liquid reaction medium need not contain any solvent for polymer of high molecular weight even at the later stages of the reaction, although if it does not the product is of relatively low molecular weight unless the final stage of polymerisation is carried out in the melt; this may be explained if the molecular chains of the polymer cease to grow in the solid state.

If the polymerisation reaction is carried out in the presence of a diluent, the reaction mixture may become solid as the polymeric product becomes insoluble. Since this may lead to non-uniform polymerisation reaction, it is desirable to maintain the product in solution by for example raising the temperature as the polymerisation proceeds.

The vessel used should be made of or lined with a material that is inert to alkali metal phenoxides and also to alkali metal halides under the conditions employed. For example, glass is unsuitable as it tends to react with phenoxide anions at high temperatures, upsetting the stoichiometry of the polymerisation and contaminating the product with silicate. Some grades of stainless steel undergo surface crazing at these temperatures in the presence of alkali metal halide, and vessels made of or lined with titanium or nickel or an alloy thereof or some similarly inert material are preferable.

This polymerisation may conveniently be carried out in an extruder or on a heated metal band.

To neutralise any reactive anionic endgroups in the polymer, a reagent therefor may be introduced at the termination of the polymerisation. Reactive monofunctional halides, for example methyl chloride, are particularly suitable.

The alkali metal halide can be removed from the resultant high polymer by any suitable means. For example, it can be extracted from the high polymer using water, or the polymer itself can be dissolved in a strongly polar organic solvent (for example dimethyl formamide, 1-methyl-2-oxo-pyrrolidine, dimethyl sulphoxide, 1,1-dioxothiolan or nitrobenzene) and then reprecipitated by addition to a liquid such as water which is miscible with the polymer solvent but is itself a non-solvent for the polymer.

When the polymer is formed in solution, a convenient procedure is to add the reaction mixture (which may be decanted or filtered from solid alkali metal halide) to an excess of a liquid which is miscible with the reaction solvent but in which the polymer is insoluble. If the reaction solvent is water-miscible, or is miscible with a liquid in which residual alkali metal halide also dissolves, the polymer can thus be obtained in one step. Otherwise, as for example if the reaction mixture is poured into methanol, the precipitated polymer initially contains alkali metal halide which can subsequently be washed out with water. An alternative procedure is to add to the reaction mixture an inert solvent such as for example bis(4-chlorophenyl)sulphone, bis(4-methylphenyl)sulphone, diphenyl sulphone which is liquid at the reaction temperature but solid at the temperature at which the polymer is subsequently processed. This procedure enables the reaction solvent to be removed by for example distillation under reduced pressure. The resulting hot polymer solution may then be allowed to cool and solidify and after being pulverised the inert solvent and unwanted reaction products may be extracted by washing with for example water, methanol, acetone.

The new aromatic polymers of the invention may also be made by the polycondensation of a carbonyl chloride of the formula ##STR15## in the presence of a Friedel-Crafts catalyst, and copolymers may be made with sulphonyl or carbonyl chlorides, for example those of the formulae ##STR16## Suitable procedures for such copolymerisations are described in British specifications 971 227, 1 016 245, 1 060 546, 1 086 021, 1 109 842 and 1 122 192.

The reduced viscosity of the polymer is desirably at least 0.3 (measured at 25° C. on a solution of the polymer in a solvent such as dimethyl formamide, N-methyl pyrrolidone or concentrated sulphuric acid containing 1 g of polymer in 100 cm³ of solution i.e. 1% w/v) if it is to serve for structural purposes as a thermoplastic. In general the new thermoplastic polymers of this invention may be used in any of the ways described for similar thermoplastic aromatic polysulphones in British specification 1 016 245. Because many of the polymers may be obtained in crystalline form, they may be of particular value in the form of film and fiber for use at high temperatures.

The following examples illustrate the invention.

The glass to rubber transition temperatures (Tg) and crystalline melting points (Tm) were determined by differential scanning calorimetry with a Perkin Elmer DSC 1B instrument calibrated by standard melting point substances at a heating rate of 16° C./min. The values of Tm were measured on powdered polymers as prepared at the maximum of the endotherm and do not represent the maximum melting point for any particular copolymer which could be attainable after suitable heat treatment. The endotherms were frequently broad especially where the crystallinity is low, as shown by X-ray methods. The values of Tg were measured at the start of the process on all copolymers in the amorphous state. Those that were originally crystalline were first cooled at 64° C./min from above their melting points to obtain them in an amorphous state (unless crystallisation from the melt was too fast).

The Tm and Tg data show the general effect of copolymer composition on the melting and softening characteristics. The melting distribution and Tg values at any copolymer composition can vary with the prior thermal treatment and distribution of comonomer units.

EXAMPLE 1

Bis-[ 4-(4-chlorobenzoyl)biphenylyl]carbonate (A) and the potassium salt of 4-(4-chlorophenylsulphone) phenol (as 1.3 mole solution in dimethyl sulphoxide) were charged (in amounts shown in Table 1) together with diphenyl sulphone (60 g), dimethyl sulphoxide (100 cm³ as indicated in Table 1) and aqueous potassium hydroxide solution (6.84 g; 0.06 moles) to a three-necked round bottomed flask (capacity 500 cm³) fitted with a stirrer, pocketed thermometer, dry nitrogen inlet, vacuum distillation head, condenser and receiver.

                  TABLE 1                                                          ______________________________________                                                                  Potassium                                                                      salt of 4-                                                                     hydroxy-                                                                       4'-chloro-                                                                               Volume of                                   Copolymer Composition:   diphenyl  dimethyl                                    Proportion of units                                                                          Carbonate  sulphone  sulphoxide                                  (a) and (b)   A          charged*  added                                       (a)     (b)       (g)    Moles Moles   cm.sup.3                                ______________________________________                                         0       1.00      --     --    0.050    0                                      0.33    0.67       6.43  0.010 0.040   100                                     0.46    0.54       9.65  0.015 0.035   100                                     0.67    0.33      16.08  0.025 0.025   100                                     0.75    0.25      19.29  0.030 0.020   100                                     ______________________________________                                          *Charged as a 1.3 molar solution in dimethyl sulphoxide.                 

The reactants were heated to 150° C. whilst being stirred under atmospheric pressure and then the pressure was carefully reduced so that water and then dimethyl sulphoxide distilled. When distillation of dimethyl sulphoxide was complete, the temperature of the reaction mixture was raised to 240° C. and the pressure returned to atmospheric by the admission of nitrogen into the flask when diphenyl sulphone started to reflux.

After polymerisation for 24 hours, the reaction mixture was cooled, removed from the flask and then mascerated with methanol (ca. 1.5 dm³). The resulting material was extracted with boiling methanol/water mixture (7:2 v/v), boiling water and boiling methanol/acetone mixture (2:1 v/v) and dried at 120° C. under reduced pressure. The polymers consisted of repeat units having the formulae ##STR17##

The polymers obtained by this procedure had the reduced viscosities (measured on 1% w/v solutions at 25° C. in (i) dimethyl formamide (ii) N-methyl pyrrolidone and (iii) concentrated sulphuric acid), glass to rubber transition temperatures (Tg), and crystalline melting points (Tm) shown in Table 2. The degree of crystallinity as shown by X-ray methods decreased progressively with increasing proportion of the sulphone component. The nature of the film compression moulded from the polymers is also indicated in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     Copolymer composition:        Compress-                                        Proportion of units           ion                                              (a) and (b) Reduced viscosity                                                                         Tm     moulded                                          a     b     (i) (ii)                                                                              (iii)                                                                              (°C.)                                                                          film                                             __________________________________________________________________________     0     1.00  0.55                                                                               -- --  NC     Tough                                            0.33  0.67  NS  -- 0.42                                                                               345-373 VB                                                                            Brittle                                          0.46  0.54  NS  -- 0.42                                                                               365 VB Brittle                                          0.67  0.33  NS  NS 0.30                                                                               366    Brittle                                          0.75  0.25  NS  NS 0.24                                                                               370    Brittle                                          1.00  0     NS  NS 0.51                                                                               418    Brittle                                          __________________________________________________________________________      NS -- not soluble or incompletely soluble                                      NC -- not crystalline                                                          VB -- very broad (approximate beginning and end of melting recorded)     

EXAMPLE 2

Bis[4-(4-chlorobenzoyl)biphenylyl]carbonate (A) and bis[4-(4-chlorophenylsulphonyl)biphenylyl] carbonate (B) were charged (in amounts given in Table 3) together with dimethyl sulphoxide (125 cm³), diphenyl sulphone (125 g) and aqueous potassium hydroxide solution (22.49 g; 0.20 moles) to a round bottomed flask (capacity 500 cm³) as described in Example 1.

                  TABLE 3                                                          ______________________________________                                         Copolymer                        Polymer-                                      composition:                     isation                                       Proportion of                                                                             Carbonate  Carbonate  conditions                                    units (a) and (c)                                                                         (A)        (B)        Temp.  Time                                   a      c       g      Moles g    Moles (°C.)                                                                          (hrs)                            ______________________________________                                         0      1.00    --     --    35.75                                                                               0.0500                                                                               200    18                               0.10   0.90    3.22   0.0050                                                                               32.16                                                                               0.0450                                                                               200    19                               0.20   0.80    6.43   0.0100                                                                               28.60                                                                               0.0400                                                                               200    18                               0.33   0.67    10.61  0.0165                                                                               23.95                                                                               0.0335                                                                               200    18                               0.40   0.60    12.86  0.0200                                                                               21.45                                                                               0.0300                                                                               200    17                               0.50   0.50    16.10  0.0250                                                                               17.90                                                                               0.0250                                                                               220-260                                                                               19                               0.67   0.33    21.54  0.0335                                                                               11.80                                                                               0.0165                                                                               200-260                                                                               21                               0.80   0.20    25.72  0.0400                                                                                7.15                                                                               0.0100                                                                               240    18                               1.00   0       32.2   0.0500                                                                               --   --    325     4                               ______________________________________                                    

The reactants were heated to 150° C. whilst being stirred under atmospheric pressure and then the pressure was carefully reduced so that water and then dimethyl sulphoxide distilled. When distillation of dimethyl sulphoxide was complete, the temperature of the reaction mixture was raised to the polymerisation temperature given in Table 3, and the pressure returned to atmospheric by the admission of nitrogen into the flask when the diphenyl sulphone started to reflux.

When the polymerisation was complete, the reaction mixture was cooled, removed from the flask and then mascerated with methanol (ca 1.5 dm³). The resulting material was extracted with boiling methanol-water (7:2 v/v), boiling water and boiling methanol-acetone (2:1 v/v) and dried at 120° C. under reduced pressure. The polymers consisted of repeating units having the formulae ##STR18##

The polymers obtained by this procedure had the reduced viscosities (measured on 1% w/v solutions at 25° C. in (i) dimethyl formamide (ii) N-methyl pyrrolidone and (iii) concentrated sulphuric acid), glass to rubber transition temperatures (Tg), and crystalline melting points (Tm) shown in Table 4. The degree of crystallinity as shown by X-ray methods decreased with increasing proportion of the sulphone component. The nature of the film compression moulded from the polymers is also indicated in Table 4.

                  TABLE 4                                                          ______________________________________                                         Copolymer                                                                      composition:                                                                   Proportion of                        Com-                                      units                                pression                                  (a) and (c)                                                                              Reduced viscosity                                                                           Tg     Tm     moulded                                    a    c       (i)    (ii) (iii)                                                                               (° C)                                                                        (°C.)                                                                          film                                ______________________________________                                         0     1.00    1.56   --   --   275  NC     Tough                               0.10  0.90    0.51   --   --   268  NC     Tough                               0.20  0.80    0.57   0.88 1.13 259  NC     Tough                               0.33  0.67    --     1.01 1.45 253  320-360                                                                               Tough                                                                   VB                                         0.40  0.60    NS     0.77 1.10 239  320-360                                                                               Tough                                                                   VB                                         0.50  0.50    NS     NS   1.26 234  365    Tough                               0.67  0.33    NS     NS   0.75 220  390    Tough                               0.80  0.20    NS     NS   0.34 ND   396    Brittle                             1.00  0       NS     NS   0.51 ND   418    Brittle                             ______________________________________                                          ND -- not detected owing to crystallinity                                      NS -- not soluble or not completely soluble                                    NC -- not crystalline                                                          VB -- very broad (approximate beginning and end of melting recorded)     

EXAMPLE 3

Bis[4-(4-chlorobenzoyl)biphenylyl]carbonate (A) and bis[4-(4-chlorobenzoyl)phenylyl] carbonate (C) were charged (in amounts given in Table 5) together with dimethyl sulphoxide (125 cm³), diphenyl sulphone (125 g) and aqueous potassium hydroxide solution (22.47 g; 0.20 moles) in a round bottomed flask (capacity 500 cm³) as described in Example 1.

The reactants were heated to 150° C. whilst being stirred under atmospheric pressure and then the pressure was carefully reduced so that water and then dimethyl sulphoxide distilled. When distillation of dimethyl sulphoxide was complete, the temperature of the reaction mixture was raised to the polymerisation temperature given in Table 5, and the pressure returned to atmospheric by the admission of nitrogen into the flask when the diphenyl sulphone started to reflux.

When the polymerisation was complete, the reaction mixture was cooled, removed from the flask and then mascerated with methanol (ca 1.5 dm³). The resulting material was extracted with boiling methanol-water (7:2 v/v), boiling water and boiling methanol-acetone (2:1 v/v) and dried at 120° C. under reduced pressure. The polymers consisted of repeat units having the formula ##STR19##

The polymers obtained by this procedure had the reduced viscosities (measured on 1% w/v solutions at 25° C. in concentrated sulphuric acid) shown in Table 5. The polymers were compression moulded into film.

                                      TABLE 5                                      __________________________________________________________________________                                              Reduced                               Copolymer composition:          Polymerisation                                                                          Viscosity                             Proportion of units             Conditions                                                                              1% w/v in                             (a) and (d) Carbonate A                                                                              Carbonate C                                                                              Temp.                                                                              Time c.Sulphuric                           a     d     g    Moles                                                                               g    Moles                                                                               (°C.)                                                                       (hours)                                                                             acid at 25° C.                 __________________________________________________________________________     0     1.00  --   --   24.55                                                                               0.0500                                                                              378 1    0.50                                  0.33  0.67  10.61                                                                               0.0165                                                                              16.45                                                                               0.0335                                                                              340 3    0.48                                  0.67  0.33  21.54                                                                               0.0335                                                                               8.10                                                                               0.0165                                                                              345 2    0.53                                  1.00  0     32.2 0.0500                                                                              --   --   325 4    0.51                                  __________________________________________________________________________ 

What we claim is:
 1. An aromatic polymer whose molecular chains consist essentially of units of the formula ##STR20## alone or copolymerised with other units obtained by elimination of alkali metal halide from a member of the group consisting of alkali metal salts of other activated halophenols and mixtures of alkali metal salts of dihydric phenols with activated dihalobenzenoid compounds in which the halogen atoms in the halophenol or dihalobenzenoid compounds are activated by electron-attracting group selected from --CO-- and --SO₂ ortho or para to the halogen atom.
 2. An aromatic polymer consisting essentially of units selected from at least one of the formulae ##STR21## at least some of said units being ##STR22## units.
 3. An aromatic polymer according to claim 2 whose molecular chains consisting essentially of units of the formula ##STR23## copolymerised with units of the formula ##STR24##
 4. An aromatic polymer according to claim 2 whose molecular chains consisting essentially of units of the formula ##STR25## copolymerised with units of the formula ##STR26##
 5. An aromatic polymer according to claim 2 whose molecular chains consisting essentially of units of the formula ##STR27## copolymerised with units of the formula ##STR28##
 6. An aromatic polymer according to claim 2 consisting essentially of units of the formula ##STR29##
 7. An aromatic copolymer consisting essentially of units of the formula ##STR30## together with untis selected from at least one of units (A) and units (B), said units A being selected from at least one of the formulae ##STR31## and said units (B) being selected from at least one of the formulae ##STR32## said units B comprising 0 to 80% of the number of units A.
 8. An aromatic copolymer consisting essentially of units of the formula ##STR33## and units consisting essentially of a chain containing benzenoid groups, oxygen or sulphur atoms and bivalent electron attracting groups separated from an oxygen or sulphur atom by a para or ortho phenylene group.
 9. An aromatic copolymer according to claim 8 in which the bivalent electron attracting groups are selected from --SO₂ -- and --CO-- groups. 